Pesticidal 1-arylpyrazole derivatives

ABSTRACT

The invention relates to novel arylpyrazoles of the formula (I): ##STR1## wherein R 1 , R 3 , R 7 , R 14 , R 15 , R 16 , and R 17  are as defined in the description, and to their use as pesticides.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of application Ser. No. 08/761,982,filed Dec. 11, 1996, now U.S. Pat. No. 5,817,688 incorporated byreference herein in its entirety and relied upon, which claims thepriority of United States Provisional Patent Applications No.60/008,869, filed Dec. 19, 1995 (Attorney Docket No. 022650-325) and No.60/028,520, filed Oct. 18, 1996 (Attorney Docket No. 022650-357), bothof which are incorporated by reference herein in their entireties andrelied upon.

The present invention relates to novel arylpyrazoles, compositionscontaining them, processes for their preparation, and their uses asinsecticides and nematicides.

This invention relates to 1-arylpyrazole derivatives. to compositionscontaining them and to the use of said compounds and compositionsagainst arthropods, particularly insects and nematodes.

U.S. Pat. No. 5,232,940 describes N-phenylpyrazoles with, among others,5-cycloalkylcarbonyl and 5-alkoxycarbonyl substituents.

DE 3509567 and EP 382034 describe 3-nitro-1-phenylpyrazoles asherbicides and insecticides.

DE 2701091 describes fungicidal pyrazoles with amides at positions 4 or5.

EP 202169 describes 1-(4-alkoxy)phenyl pyrazoles as herbicides.

EP 398499 describes cyano-phenylpyrazoles as insecticides.

None of the foregoing publications describes or suggests that compoundsof formula (I) possess or would be expected to possess activity againstarthropods, especially insects or nematodes.

This invention provides novel arylpyrazoles of the formula (I): ##STR2##wherein: R₁ is selected from cyano, halogen, formyl, C(O)R₂, H, and R₂ ;

R₂ is selected from C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, and cycloalkyloptionally substituted with one or more halogens;

R₃ is selected from halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, nitro,CONR₄ R₅, COOR₄, and --S(O)_(n) R₆ ;

R₄ and R₅ are independently selected from H, C₁ -C₅ alkyl, and C₁ -C₅haloalkyl;

R₆ is selected from C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, and cycloalkyloptionally substituted with one or more halogens;

R₇ is selected from C(O)R₈, C₁ -C₆ α-hydroxyalkyl, C₁ -C₆α-hydroxyhaloalkyl, C(OR₉)═CHR₁₀, CHR₁₁ R₁₂, --CR₁₃ ═ND and ##STR3## R₈is selected from H, C₁ -C₅ alkyl, and C₁ -C₅ haloalkyl;

R₉ is selected from C(O)R₁₈, CHO, --S(O)₂ R₁₈, --S(O)₂ aryl, C₃ -C₁₈trialkylsilyl, C₈ -C₁₈ dialkylarylsilyl, C₁₃ -C₂₀ diarylalkylsilyl andC₁₈ -C₂₄ trialkylsilyl;

R₁₀ is selected from H, C₁ -C₄ alkyl, and C₁ -C₄ haloalkyl;

R₁₁ and R₁₂ are independently selected from C₁ -C₄ alkoxy, C₁ -C₄haloalkoxy, C₁ -C₄ alkylthio, C₁ -C₄ haloalkylthio, NR₈ R₁₀, C₃ -C₈trialkylsiloxy and cyano;

R₁₃ is selected from H, C₁ -C₅ allyl, and C₁ -C₅ haloalkyl;

R₁₄ is selected from H, halogen, C₁ -C₄ allyl, C₁ -C₄ haloalkyl, C₁ -C₄alkoxy, C₁ -C₄ haloalkoxy, C₁ -C₄ alkylthio, C₁ -C₄ haloalkylthio, cyanoand nitro;

R₁₅ and R₁₇ are independently selected from H and halogen;

R₁₆ is selected from halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄alkoxy, C₁ -C₄ haloalkoxy, cyano, nitro, C(O)R₁₈, and --S(O)_(q) R₁₉ ;

R₁₈ is selected from C₁ -C₃ alkyl and C₁ -C₃ haloalkyl;

R₁₉ is selected from C₁ -C₃ alkyl and C₁ -C₃ haloalkyl;

X is selected from a nitrogen atom or C--R₂₀ ;

R₂₀ is selected from H, halogen, cyano, nitro, C₁ -C₄ alkyl, C₁ -C₄haloalkyl, C₁ -C₄ alkoxy, and C₁ -C₄ haloalkoxy;

A and E are independently selected from NR₂₁, O and S;

R₂₁ is selected from H, C₁ -C₄ alkyl and C₁ -C₄ haloalkyl;

D is selected from OR₂₂ and NR₂₃ R₂₄ ;

R₂₂, R₂₃ and R₂₄ are independently selected from H, C₁ -C₄ alkyl, and C₁-C₄ haloalkyl;

Z is (CH₂)_(m) ;

m is 2, 3 or 4;

n is 0, 1 or 2;

q is 0, 1 or 2;

and pesticidally acceptable salts thereof;

provided that:

R₁₁ and R₁₂ are always the same except when R₁₂ is cyano; and

R₄ is not H when R₃ is COOR₄.

By the term "pesticidally acceptable salts" is meant salts the anions ofwhich are known and accepted in the art for the formation ofpesticidally acceptable salts. Preferably such salts are water soluble.Suitable acid addition salts, formed by compounds of formula (I)containing an amine group, include salts with inorganic acids, forexample hydrochlorides, phosphates, sulfates, nitrates; and salts withorganic acids, for example acetates.

In this specification, "halogen" means the atoms fluorine, chlorine,bromine and iodine. Alkyl groups and moieties may be either linear orbranched chain. "Cycloalkyl" means a cycloalkyl group having from threeto seven carbon atoms in the ring, each of which optionally bears one ormore C₁ -C₄ alkyl "Aryl" means phenyl optionally substituted by one ormore of the members of the group consisting of C₁ -C₄ alkyl and halogenwhich may be the same or different. It will be understood that incertain cases, compounds of formula (I) can be present in the form ofoptical and/or stereoisomers. All such forms are embraced by theinvention.

Compounds of formula (I) above in which R₇ is formyl generally possess alower level of activity as insecticides but are useful as intermediatesin the preparation of more highly active species.

It will be understood that the provisos appearing in the abovedescription are present for reasons of biological efficacy and syntheticaccessibility.

A feature of the invention are those compounds having one or more of thefollowing features:

R₁ is cyano;

R₃ is --S(O)_(n) R₆ ;

R₇ is selected from the group C(O)R₈, C₁ -C₆ α-hydroxyalkyl, C₁ -C₆α-hydroxyhaloalkyl, C(OR₉)═CHR₁₀, CHR₁₁ R₁₂, and --CR₁₃ ═ND;

R₁₄ is halogen;

R₁₅ and R₁₇ are H;

R₁₆ is C₁ -C₄ haloalkyl; and

X is C--R₂₀.

Preferred compounds of formula (I) above are compounds wherein:

R₁ is selected from cyano, halogen, C(O)R₂, H, and R₂ ;

R₃ is --S(O)_(n) R₆ ;

R₇ is selected from C(O)R₈, --CR₁₃ ═ND, and --CHR₁₁ R₁₂ ;

R₁₄ is halogen;

R₁₅ and R₁₇ are H; and

R₁₆ is C₁ -C₄ haloalkyl.

A further preferred class of compounds of formula (I) are those wherein:

R₁ is cyano;

R₃ is --S(O)_(n) R₆ ;

R₆ is C₁ -C₂ haloalkyl, preferably CF₃ ;

R₇ is selected from C(O)R₈, --CHR₁₁ R₁₂ and --CR₁₃ ═ND;

R₁₁ is C₁ -C₄ alkoxy;

R₁₂ is selected from C₁ -C₄ alkoxy and cyano;

R₁₄ is halogen;

R₁₅ and R₁₇ are H;

R₁₆ is C₁ -C₂ haloalkyl, especially CF₃.

The numbers 1-21 are assigned to these compounds for reference andidentification. Hereinafter compounds of formula (I) include thefollowing:

1.5-Acetyl-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulfonylpyrazole,m.p. about 161° C.;

2.3-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-formyl-4-trifluoromethylthiopyrazole,m.p. about 90° C.;

3.5-{(N-amino)iminomethylidenyl}-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylthiopyrazole,m.p. about 130° C.;

4.3-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-dimethoxymethyl-4-trifluoromethylthiopyrazole,m.p. about 93° C.;

5.3-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-{(N-methoxy)iminomethylidenyl}-4-trifluoromethylthiopyrazole,m.p. about 87° C.;

6.3-Cyano-5-{(1-cyano-1-methoxy)methyl}-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-triuoromethylthiopyrazole,an oil;

7.3-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(hydroxy)methyl-4-trifluoromethylthiopyrazole,m.p. about 118° C.;

8.3-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(1-hydroxy)ethyl-4-trifluoromethylthiopyrazole,m.p. about 123° C.;

9.5-Acetyl-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylthiopyrazole,m.p. about 128° C.;

10.5-Acetyl-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulfinylpyrazole,m.p. 156° C.;

11.3-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(N,N-dimethylaminoiminomethylidenyl)-4-trifluoromethylthiopyrazole,m.p. about 126° C.;

12.3-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(hydroxy)methyl-4-trifluoromethylsulfinylpyrazole,m.p. about 153° C.;

13.3-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-dimethoxymethyl-4-trifluoromethylsulfinylpyrazole,m.p. about 116° C.;

14.3-Cyano-5-{(1-cyano-1-methoxy)methyl}-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulfinylpyrazole,m.p. about 167° C.;

15.3-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-dimethoxymethyl-4-trifluoromethylsulfonylpyrazole,m.p. 137° C.;

16.3-Cyano-5-{(1-cyano-1-methoxy)methyl}-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulfonylpyrazole,m.p. 90° C.;

17.3-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(1-hydroxy-2,2,2-trifluoroethyl)-4-trifluoromethylthiopyrazole,m.p. about 106° C.;

18.3-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-diethoxymethyl-4-trifluoromethylthiopyrazole,m.p. about 72° C.;

19.3-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-diethoxymethyl-4-trifluoromethylsulfonylpyrazole,m.p. about 100° C.;

20.3-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-diethoxymethyl-4-trifluoromethylsulfinylpyrazole,m.p. 132° C.;

21.3-Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(1-acetoxyethenyl)-4-trifluoromethylsulfonylpyrazole,m.p. 121° C.;

It is an object of the present invention to provide new pesticidalcompounds of the 1-arylpyrazole family together with processes for theirpreparation.

A second object of the present invention is to provide pesticidalcompositions and pesticidal methods of use of the pesticidal pyrazolecompounds against arthropods, especially insects, plant nematodes, orhelminth or protozoan pests, particularly in agricultural orhorticultural crops, forestry, veterinary medicine or livestockhusbandry, or in public health.

A third object of the present invention is to provide very activecompounds, with broad spectrum pesticidal activity, as well as compoundswith selective special activity, e.g., aphicidal, foliar insecticidal,soil insecticidal and nematicidal, systemic, antifeeding or pesticidalactivity via seed treatment.

A fourth object of the present invention is to provide compounds withsubstantially enhanced and more rapid activity, especially againstinsects and more particularly insects in their larval stages.

A fifth object of the present invention is to provide compounds withgreatly improved (greater and faster) penetration into pest species whentopically applied and thus to provide enhanced movement of the compoundsto the pesticidal site(s) of action within the pest.

Another object of the present invention is to provide compounds withhigh activity and improved safety to the user and the environment, whichare obtained by optimization of chemical, physical and biologicalproperties such as solubility, melting point, stability, electronic andsteric parameters, and the like.

These objects are achieved, in whole or in part, by the presentinvention.

The compounds of formula (I) can be prepared by the application oradaptation of known methods (i.e., methods heretofore used or describedin the chemical literature): generally pyrazole ring formation followedwhere necessary by changing substituents. It is also to be understoodthat, in the description of the following processes the sequences forthe introduction of the various groups on the pyrazole ring may beperformed in a different order and that suitable protecting groups maybe required as will be apparent to those skilled in the art.

In the following description of processes when symbols appearing informulae are not specifically defined, it is to be understood that theyare "as defined above" in accordance with the first definition of eachsymbol in this specification. The term "protection" shall includeconversion to a suitable non-reactive group which may be reconvertedwhen desired, as well as the addition of groups which render thefunctionality non-reactive.

In the description that follows, the ring system: ##STR4## is defined asQ.

According to a feature of the present invention compounds of formula (I)wherein R₇ is formyl are formed by oxidative cleavage of the alkenemoiety of a compound of formula (II): ##STR5## wherein R₂₅ is selectedfrom alkylcarbonyl, alkoxycarbonyl, cyano and nitro. When R₂₅ isalkylcarbonyl or alkoxycarbonyl, it is preferably (C₁ -C₁₂alkyl)carbonyl or (C₁ -C₁₂ alkoxy)carbonyl, most preferably (C₁ -C₆alkyl)carbonyl or (C₁ -C₆ alkoxy)carbonyl. Such a transformation is wellknown to those skilled in the art and can be realized with ozone,potassium permanganate, sodium metaperiodate and the like. The processmay be carried out optionally in a solvent such as methylene chloride,diethyl ether or chloroform and generally at temperatures between -100°C. and 100° C. A summary of such methods is found in ComprehensiveOrganic Transformations, VCH Publishers, 1989, R. C. Larock, pp.595-596.

Compounds of formula (II) are novel and constitute a further feature ofthe invention. Compounds of formula (II) can be prepared bydehydrohalogenation of a compound of formula (III): ##STR6## wherein"halo" represents halogen and R₂₅ is defined as above.

This can be effected by reaction of formula (III) compounds with basessuch as triethylamine, sodium hydroxide and lithium diisopropylamide.The reaction is carried out optionally in a common organic solvent suchas dichloromethane, diethyl ether, tetrahydrofuran, or toluene, andgenerally between -100 and 100° C. depending on the base used. Compoundsof formula (III) are novel and constitute a further feature of theinvention.

Compounds of formula (III) can be produced from compounds of formula(IV): ##STR7##

The process is effected by reaction of a compound of formula (IV) withan olefin of formula (V) in the presence of an alkylnitrite and Copper(II) halide, for example, as described in J. Org. Chem., 1977, 42 (14)2431. Those skilled in the art will recognize this as a MeerweinArylation. The process is generally carried out in a mixture of theolefin and a common organic solvent, preferably acetonitrile. Theprocess is generally carried out at a temperature from -50 to 100° C.,preferably at ambient temperature.

Syntheses of compounds of formula (IV) are described in U.S. Pat. Nos.5,232,940; 5,306,694; 4,772,312; 4,804,675; and 4,614,533.

According to a further feature of the present invention, compounds offormula (I) above in which R₇ is --CHR₁₁ R₁₂ wherein R₁₁ and R₁₂ are notcyano and are the same, or in which R₇ is ##STR8## may be prepared bythe reaction of the corresponding compound of formula (I) above in whichR₇ is formyl with a compound of formula (VIa) or (VIb) respectively,wherein R₁₁ is not cyano: ##STR9## in the presence of a catalyst, suchas sulfuric acid, hydrochloric acid, para-toluenesulfonic acid, anacidic resin or a Lewis acid catalyst such as zinc (II) chloride. Theprocess is generally carried out optionally in the presence of a solventsuch as dichloromethane or benzene and occurs from -20° C. to 100° C.,preferably at the boiling point of the solvent. Those skilled in the artwill recognize this reaction as an acetal formation, the generalconditions of which are found in Protective Groups in Organic Synthesis,2nd Ed., Wiley-Interscience, 1991, T. W. Greene and P. G. M. Wuts, pp.175-220. Compounds of formulae (VIa) and (VIb) are known to thoseskilled in the art as alcohols, amines and thiols.

According to a further feature of the present invention, compounds offormula (I) above in which R₇ is --CHR₁₁ (CN) may be prepared from thecorresponding compound of formula (I) in which R₇ is --CHR₁₁ R₁₂ inwhich R₁₁ and R₁₂ are the same, by treatment with a trialkylsilylcyanidein the presence of an acid catalyst, preferably a Lewis acid catalyst,e.g. a group IIB, IIA, or IVA halide, such as titanium tetrachloride, ina solvent such as dichloromethane or acetonitrile. Such a process iscarried out from -30 to 100° C., preferably from 0° to -20° C. and isdescribed in Tetrahedron Lett., 1984, 25 (31) 3301; Chem. Lett., 1984,897, and Bull. Chem. Soc. Jpn., 1990, 63, 3122.

According to a further feature of the present invention, compounds offormula (I) above in which R₇ is C₁ -C₆ α-hydroxyalkyl or C₁ -C₆α-hydroxyhaloalkyl may be prepared by the reaction of the correspondingcompound of formula (I) in which R₇ is formyl with an organometallicreagent or hydride of formula R₈ --M, wherein M is an alkali ortransition metal. The reaction may be performed in a solvent such as adialkyl ether (e.g. diethyl ether), tetrahydrofuran (THF), or ahydrocarbon (e.g. hexane or toluene) or mixtures thereof. A temperatureof from -100° C. to the reflux temperature of the solvent system isgenerally used.

According to a further feather of the present invention, compounds offormula (I) above in which R₇ is C(O)R₈ may be prepared by the oxidationof a compound of formula (I) wherein R₇ is C₁ -C₆ α-hydroxyalkyl or C₁-C₆ α-hydroxyhaloalkyl.

This is a reaction well known to those skilled in the art, a summary ofwhich is given in Comprehensive Organic Transformation, VCH Publishers,1989, R. C. Larock, pp. 604-614.

According to a further feature of the present invention, compounds offormula (I) in which R₇ is CR₁₃ ═ND may be prepared by the reaction ofthe corresponding compound of formula (I) in which R₇ is C(O)R₈respectively with a compound of formula (VII):

    D--NH.sub.2                                                (VII)

The process is generally carried out optionally in the presence of asolvent such as ethanol, methylene chloride, or toluene and generally attemperatures between 0° C. and the reflux temperature of the solvent.Those skilled in the art will recognize such reactions as formations ofoximes and hydrazones whose methods of synthesis are reviewed inAdvanced Organic Chemistry, 4th ed., J. Wiley and Sons, 1992, March, pp.804-806. Compounds of formula (VII) are well known to those skilled inthe art or may be prepared by known methods.

According to a further feature of the present invention, compounds offormula (I) above in which R₇ is --C(OR₉)═CHR₁₀ may be prepared by thereaction of the corresponding compound of formula (I) in which R₇ isC(O)R₈ (and R₈ is not H) with a base, followed by treatment with acompound of formula R₉ --L, wherein L is a leaving group, such as halideanion or sulfonate anion. Suitable bases include triethylamine andlithium diisopropylamide. The process is generally carried out within arange of temperatures, usually between -100° C. and the boilingtemperature of the solvent, such as tetrahydrofuran, toluene, diethylether and the like. Modern Organic Chemistry, 2nd ed., BenjaminCummings, 1972, H. O. House, p. 763 describes a similar process.

Pesticidally acceptable salts of the compounds of formula (I) may beprepared by known methods.

The following compounds are further examples of the invention. In thetable that follows the following abbreviations have been used:

                  TABLE I    ______________________________________    1 #STR10##    R.sub.3    X               R.sub.7    ______________________________________    SCF.sub.3  C-Cl            COEt    SCF.sub.3  C-Cl            COPr    SCF.sub.3  C-Cl            CH(OEt)CN    SCF.sub.3  C-Cl            CH═NOH    SOCF.sub.3 C-Cl            COEt    SOCF.sub.3 C-Cl            COPr    SOCF.sub.3 C-Cl            CH(OEt)CN    SOCF.sub.3 C-Cl            CH═NOH    SOCF.sub.3 C-Cl            CH═NNH.sub.2    SO.sub.2 CF.sub.3               C-Cl            COEt    SO.sub.2 CF.sub.3               C-Cl            COPr    SO.sub.2 CF.sub.3               C-Cl            CH(OEt)CN    SO.sub.2 CF.sub.3               C-Cl            CH═NOH    SO.sub.2 CF.sub.3               C-Cl            CH═NNH.sub.2    SCCl.sub.2 F               C-Cl            COEt    SCCl.sub.2 F               C-Cl            COPr    SCCl.sub.2 F               C-Cl            CH(OMe).sub.2    SCCl.sub.2 F               C-Cl            CH(OEt).sub.2    SCCl.sub.2 F               C-Cl            CH(OMe)CN    SCCl.sub.2 F               C-Cl            CH═NOH    SCCl.sub.2 F               C-Cl            CH═NNH.sub.2    SCCl.sub.2 F               C-Cl            COMe    SOCCl.sub.2 F               C-Cl            COMe    SOCCl.sub.2 F               C-Cl            COEt    SOCCl.sub.2 F               C-Cl            COPr    SOCCl.sub.2 F               C-Cl            CH(OMe).sub.2    SOCCl.sub.2 F               C-Cl            CH(OEt).sub.2    SOCCl.sub.2 F               C-Cl            CH(OMe)CN    SOCCl.sub.2 F               C-Cl            CH═NOH    SOCCl.sub.2 F               C-Cl            CH═NNH.sub.2    SO.sub.2 CCl.sub.2 F               C-Cl            COMe    SO.sub.2 CCl.sub.2 F               C-Cl            COEt    SO.sub.2 CCl.sub.2 F               C-Cl            COPr    SO.sub.2 CCl.sub.2 F               C-Cl            CH(OMe)    SO.sub.2 CCl.sub.2 F               C-Cl            CH(OMe)CN    SO.sub.2 CCl.sub.2 F               C-Cl            CH(OEt).sub.2    SO.sub.2 CCl.sub.2 F               C-Cl            CH═NOH    SO.sub.2 CCl.sub.2 F               C-Cl            CH═NNH.sub.2    SCF.sub.3  N               COEt    SCF.sub.3  N               COPr    SCF.sub.3  N               CH(OEt)CN    SCF.sub.3  N               CH═NOH    SOCF.sub.3 N               COEt    SOCF.sub.3 N               COPr    SOCF.sub.3 N               CH(OEt)CN    SOCF.sub.3 N               CH═NOH    SOCF.sub.3 N               CH═NNH.sub.2    SO.sub.2 CF.sub.3               N               COEt    SO.sub.2 CF.sub.3               N               COPr    SO.sub.2 CF.sub.3               N               CH(OEt)CN    SO.sub.2 CF.sub.3               N               CH═NOH    SO.sub.2 CF.sub.3               N               CH═NNH.sub.2    SCCl.sub.2 F               N               COEt    SCCl.sub.2 F               N               COPr    SCCl.sub.2 F               N               CH(OMe).sub.2    SCCl.sub.2 F               N               CH(OEt).sub.2    SCCl.sub.2 F               N               CH(OMe)CN    SCCl.sub.2 F               N               CH═NOH    SCCl.sub.2 F               N               CH═NNH.sub.2    SCCl.sub.2 F               N               COMe    SOCCl.sub.2 F               N               COMe    SOCCl.sub.2 F               N               COEt    SOCCl.sub.2 F               N               COPr    SOCCl.sub.2 F               N               CH(OMe).sub.2    SOCCl.sub.2 F               N               CH(OEt).sub.2    SOCCl.sub.2 F               N               CH(OMe)CN    SOCCl.sub.2 F               N               CH═NOH    SOCCl.sub.2 F               N               CH═NNH.sub.2    SO.sub.2 CCl.sub.2 F               N               COMe    SO.sub.2 CCl.sub.2 F               N               COEt    SO.sub.2 CCl.sub.2 F               N               COPr    SO.sub.2 CCl.sub.2 F               N               CH(OMe)    SO.sub.2 CCl.sub.2 F               N               CH(OMe)CN    SO.sub.2 CCl.sub.2 F               N               CH(OEt).sub.2    SO.sub.2 CCl.sub.2 F               N               CH═NOH    SO.sub.2 CCl.sub.2 F               N               CH═NNH.sub.2    SCF.sub.3  C-Cl            COMe    SCF.sub.3  C-Cl            COEt    SCF.sub.3  C-Cl            COPr    SCF.sub.3  C-Cl            CH(OEt)CN    SCF.sub.3  C-Cl            CH═NOH    SOCF.sub.3 C-Cl            COEt    SOCF.sub.3 C-Cl            COPr    SOCF.sub.3 C-Cl            CH(OEt)CN    SOCF.sub.3 C-Cl            CH═NOH    SOCF.sub.3 C-Cl            CH═NNH.sub.2    SO.sub.2 CF.sub.3               C-Cl            COEt    SO.sub.2 CF.sub.3               C-Cl            COPr    SO.sub.2 CF.sub.3               C-Cl            CH(OEt)CN    SO.sub.2 CF.sub.3               C-Cl            CH═NOH    SO.sub.2 CF.sub.3               C-Cl            CH═NNH.sub.2    SCCl.sub.2 F               C-Cl            COEt    SCCl.sub.2 F               C-Cl            COPr    SCCl.sub.2 F               C-Cl            CH(OMe).sub.2    SCCl.sub.2 F               C-Cl            CH(OEt).sub.2    SCCl.sub.2 F               C-Cl            CH(OMe)CN    SCCl.sub.2 F               C-Cl            CH═NOH    SCCl.sub.2 F               C-Cl            CH═NNH.sub.2    SCCl.sub.2 F               C-Cl            COMe    SOCCl.sub.2 F               C-Cl            COMe    SOCCl.sub.2 F               C-Cl            COEt    SOCCl.sub.2 F               C-Cl            COPr    SOCCl.sub.2 F               C-Cl            CH(OMe).sub.2    SOCCl.sub.2 F               C-Cl            CH(OEt).sub.2    SOCCl.sub.2 F               C-Cl            CH(OMe)CN    SOCCl.sub.2 F               C-Cl            CH═NOH    SOCCl.sub.2 F               C-Cl            CH═NNH.sub.2    SO.sub.2 CCl.sub.2 F               C-Cl            COMe    SO.sub.2 CCl.sub.2 F               C-Cl            COEt    SO.sub.2 CCl.sub.2 F               C-Cl            COPr    SO.sub.2 CCl.sub.2 F               C-Cl            CH(OMe)    SO.sub.2 CCl.sub.2 F               C-Cl            CH(OMe)CN    SO.sub.2 CCl.sub.2 F               C-Cl            CH(OEt).sub.2    SO.sub.2 CCl.sub.2 F               C-Cl            CH═NOH    SO.sub.2 CCl.sub.2 F               C-Cl            CH═NNH.sub.2    SCF.sub.3  N               COMe    SCF.sub.3  N               COEt    SCF.sub.3  N               COPr    SCF.sub.3  N               CH(OEt)CN    SCF.sub.3  N               CH═NOH    SOCF.sub.3 N               COMe    SOCF.sub.3 N               COEt    SOCF.sub.3 N               COPr    SOCF.sub.3 N               CH(OEt)CN    SOCF.sub.3 N               CHNOH    SOCF.sub.3 N               CH═NNH.sub.2    SO.sub.2 CF.sub.3               N               COMe    SO.sub.2 CF.sub.3               N               COEt    SO.sub.2 CF.sub.3               N               COPr    SO.sub.2 CF.sub.3               N               CH(OEt)CN    SO.sub.2 CF.sub.3               N               CH═NOH    SO.sub.2 CF.sub.3               N               CH═NNH.sub.2    SCCl.sub.2 F               N               COEt    SCCl.sub.2 F               N               COPr    SCCl.sub.2 F               N               CH(OMe).sub.2    SCCl.sub.2 F               N               CH(OEt).sub.2    SCCl.sub.2 F               N               CH(OMe)CN    SCCl.sub.2 F               N               CH═NOH    SCCl.sub.2 F               N               CH═NNH.sub.2    SCCl.sub.2 F               N               COMe    SOCCl.sub.2 F               N               COMe    SOCCl.sub.2 F               N               COEt    SOCCl.sub.2 F               N               COPr    SOCCl.sub.2 F               N               CH(OMe).sub.2    SOCCl.sub.2 F               N               CH(OEt).sub.2    SOCCl.sub.2 F               N               CH(OMe)CN    SOCCl.sub.2 F               N               CH═NOH    SOCCl.sub.2 F               N               CH═NNH.sub.2    SO.sub.2 CCl.sub.2 F               N               COMe    SO.sub.2 CCl.sub.2 F               N               COEt    SO.sub.2 CCl.sub.2 F               N               COPr    SO.sub.2 CCl.sub.2 F               N               CH(OMe)    SO.sub.2 CCl.sub.2 F               N               CH(OMe)CN    SO.sub.2 CCl.sub.2 F               N               CH(OEt).sub.2    SO.sub.2 CCl.sub.2 F               N               CH═NOH    SO.sub.2 CCl.sub.2 F               N               CH═NNH2    ______________________________________     Me = methyl     Et = ethyl     Pr = npropyl     Wherein: R.sub.1 = CN; R.sub.15 = R.sub.17 = H; R.sub.14 = Cl; R.sub.16 =     CF.sub.3 -

The following non-limiting EXAMPLES 1 to 15 illustrate detailed methodsof synthesis and the physical properties of representative pesticidalcompounds of formula (I) (and their chemical intermediates) according tothe invention. Additionally, one or more spectroscopic analyses (IR, H¹or F¹⁹ NMR, MS, etc.) have been performed on each compound forcharacterization and confirmation of the chemical structure.

EXAMPLE 1 Preparation of5-(2'-bromo-2'-carbomethoxy)ethyl-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylthiopyrazole

A solution of5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylthiopyrazole(100 g, 0.24 mol) and acetonitrile was added dropwise to a solution ofmethyl acrylate (430 ml, 4.78 mol), copper (II) bromide (80 g, 0.036mol), 90% tert-butylnitrite (51 ml, 0.39 mol) and acetonitrile (400 ml)at 0° C. After warming to room temperature, the reaction was stirred 12hours. The mixture was diluted with diethyl ether and washed with water.After drying over magnesium sulfate, the organic layer was concentratedunder reduced pressure. Trituration from hexanes gave the title compoundas a white solid (72.7 g) m.p. about 122° C.

EXAMPLE 2 Preparation of3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(E-2-methoxycarbonylethenyl)-4-trifluoromethylthiopyrazole

The product of Example 1 (45 g, 0.079 mol) was dissolved in toluene (60ml) and 1,8-diazabicyclo- 5,4,0!-undec-7-ene (13 ml, 0.087 mol) added.After stirring for 30 minutes, the mixture was diluted with ethylacetate, washed with water, 10% aqueous hydrochloric acid solution,saturated aqueous sodium hydrogen carbonate solution and saturatedsodium chloride solution. The organic phase was dried over magnesiumsulfate, filtered and concentrated under reduced pressure. The remainingoil was triturated under cold pentane to leave the title compound as awhite solid (36.6 g), m.p. about 90° C.

EXAMPLE 3 Preparation of3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-formyl-4-trifluoromethylthiopyrazole

Ozone was bubbled through a solution of the product of Example 2 (36.6g, 0.075 mol) in dichloromethane (1.8 L) at -78° C. After 3 hours theintensely blue solution was decolorized with oxygen gas, then treatedwith dimethylsulfide (19 ml, 0.26 mol). This was allowed to warm to roomtemperature over a 14 hour period whereupon the mixture was washed withwater, dried over magnesium sulfate, filtered and concentrated underreduced pressure to provide the title compound as white crystals (30.7g), m.p. about 90° C.

EXAMPLE 4 Preparation of3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-dimethoxymethyl-4-trifluoromethylthiopyrazole

The product of Example 3 (2.0 g, 0.005 mol) was combined withtrimethylorthoformate (10 ml, 0.09 mol) and para-toluenesulfonic acidmonohydrate (50 mg, catalytic) in anhydrous methanol. The mixture wasrefluxed for 72 hours, cooled to room temperature, poured into diethylether, washed with a 1:1 mixture of 10% aqueous sodium hydroxidesolution and concentrated aqueous sodium chloride solution (100 ml),water (100 ml) and saturated aqueous sodium chloride solution (100 ml).The organic phase was dried over magnesium sulfate, filtered andconcentrated in vacuo to leave an oil that was purified by silica gelchromatography using a 3:1 hexane:dichloromethane solvent mixture. Thisprovided the title compound as a white solid (1.83 g), m.p. about 93° C.Also prepared by this method: Compound 18.

EXAMPLE 5 Preparation of3-cyano-5-(1-cyano-1-methoxy)methyl-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylthiopyrazole

The product of Example 4 (3.0 g, 6.3 mmol) was combined withtrimethylsilylcyanide (2.5 ml, 18.9 mmol) in acetonitrile and cooled to0° C. Boron trifluoride ethereate (74 μl, 0.6 mmol) was added, themixture stirred 5 minutes and warmed to room temperature. After 1.25hours, the mixture was poured into saturated aqueous sodium hydrogencarbonate solution and washed with diethyl ether. The combined organicphases were washed with water, saturated aqueous sodium chloridesolution, dried over magnesium sulfate, filtered and concentrated underreduced pressure. Removal of solvents in vacuo provided the titlecompound as a yellow oil (2.99 g). 1H-NMR (300 MHz, CDCl₃): d 7.69 (m,2H); 5.28 (s, 1H); 3.35 (s, 3H).

EXAMPLE 6 Preparation of5-(1-O-acetylethenyl)-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulfonylpyrazole

A solution of5-bromo-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulfonylpyrazole(2.3 g, 4.4 mmol, the preparation of which is described in U.S. Pat. No.5,232,940) in anhydrous tetrahydrofuran, was cooled to -78° C. andtreated with n-butyllithium (2.12 ml of 2.5 m solution in hexanes, 5.3mmol) by dropwise addition. After 2 hours, the mixture was treated withacetyl chloride (0.37 ml, 5.3 mmol) over 10 minutes. After warming toroom temperature and stirring 14 hours, the mixture was poured onto iceand washed with diethyl ether. The combined organic phases were washedwith water, saturated aqueous sodium chloride solution, dried overmagnesium sulfate, filtered and concentrated under reduced pressure.Chromatography of the resulting oil in ethylacetate:hexanes left thetitle compound as a white solid (0.52 g), m.p. about 121° C.

EXAMPLE 7 Preparation of5-acetyl-3-cyano-1-(2,6-dichloro-4trifluoromethylphenyl)-4-trifluoromethylsulfonylpyrazole

The product of Example 6 (150 mg, 0.3 mmol) was dissolved intetrahydrofuran and treated with a 6M aqueous hydrochloric acid solution(1 ml, 6 mmol) and the resulting solution heated to reflux for 22 hours.The mixture was cooled to room temperature, washed with diethyl etherand the organic phase dried over magnesium sulfate. After filtering andconcentrating under reduced pressure, the residue was chromatographed onsilica gel with ethylacetate:hexanes to provide the title compound as awhite solid (120 mg), m.p. about 161° C.

EXAMPLE 8 Preparation of3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(1-hydroxyethyl)-4-trifluoromethylthiopyrazole

Copper (I) iodide (6.1 g, 0.032 mol) was suspended in anhydrous diethylether and cooled to 0° C. Methyllithium (1.6M in diethyl ether, 40 ml,0.064 mol) was added via cannula and stirred 10 minutes. A solution ofthe product of Example 3 (10 g, 0.023 mol) in diethyl ether was addedvia cannula creating a bright yellow suspension. After 15 minutes, 10%aqueous hydrochloric acid (40 ml) was added while venting the reactionvessel. The remaining suspension was filtered through Celite® and washedwith diethyl ether several times. The organic phase was washed withsaturated sodium hydrogen carbonate solution, saturated aqueous sodiumchloride solution, dried over magnesium sulfate, filtered andconcentrated under reduced pressure. Trituration from pentane providedcrystals that were purified by silica gel chromatography using ethylacetate:hexanes. The title compound was isolated as a white solid (7.56g), m.p. about 123° C.

EXAMPLE 9 Preparation of5-acetyl-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylthiopyrazole

The product of Example 8 (2.8 g, 0.0062 mol) was combined with Celite®(3.0 g) in dichloromethane. Pyridinium chlorochromate (1.7 g, 0.0079mol) was added in one portion and the slurry stirred 6 hours. Anotherportion of oxidant (0.9 g) was added and the mixture stirred anadditional 18 hours. The mixture was diluted with diethyl ether,filtered through Florisil®, and the filtrate concentrated under reducedpressure. The title compound was isolated as a white solid (2.72 g),m.p. about 128° C.

EXAMPLE 10 Preparation of5-acetyl-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulfinylpyrazole

The product of Example 8 (0.80 g, 118 mmol) was dissolved intrifluoroacetic acid (8 ml), cooled to 0° C. and treated with a 30%aqueous solution of hydrogen peroxide (0.18 ml, 1.8 mmol). After 14hours at 0° C., more hydrogen peroxide solution was added (0.25 ml, 2.5mmol) and the mixture stirred 14 hours at 0° C. The mixture was thenpoured into water which precipitated a white solid. This solid wasfiltered, washed with water, dissolved in dichloromethane, dried oversodium sulfate, filtered and concentrated under reduced pressure. Theresidue was purified by silica gel chromatography using an ethylacetate:hexanes solvent gradient. The title compound was isolated as awhite solid (0.4 g), m.p. about 156° C. Also prepared by this method:Compounds 12, 14, and 16.

EXAMPLE 11 Preparation of 5-(N-amino)iminomethylidenyl!-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-trifluoromethylthiopyrazole

The product of Example 3 (2.0 g, 4.6 mmol) was combined with hydrazine(0.25 ml, 7.8 mmol) in anhydrous ethanol and heated to reflux untilanalytical thin layer chromatography indicated the reaction wascomplete. The mixture was cooled to room temperature, concentrated underreduced pressure, and diluted with ethyl acetate. The organic phase waswashed with water, concentrated aqueous sodium chloride solution, driedover magnesium sulfate, filtered and concentrated under reducedpressure. Silica gel chromatography using an ethyl acetate:hexanesgradient provided the title compound as a white solid (0.44 g) m.p.about 130° C. Also prepared by this method: Compound 11.

EXAMPLE 12 Preparation of3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(N-methoxy)iminomethylidenyl!-4-trifluoromethylthiopyrazole

The product of Example 3 (1.0 g, 2.3 mmol) was combined withmethoxylamine hydrochloride (192 mg, 2.3 mmol) and sodium acetatetrihydrate (314 mg, 2.3 mmol) in anhydrous ethanol and heated to refluxfor 20 hours. The mixture was cooled to room temperature, concentratedunder reduced pressure and diluted with diethyl ether. The organic phasewas washed with water, saturated aqueous sodium chloride solution, driedover magnesium sulfate, filtered and concentrated under reducedpressure. The residue was purified by silica gel chromatography usingethyl acetate:hexanes. The title compound was isolated as a 3:1 mixtureof isomers (317 mg), m.p. about 87° C.

EXAMPLE 13 Preparation of3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-hydroxymethyl-4-trifluoromethylthiopyrazole

The product of Example 3 (5.0 g, 0.012 mol) was added to a mixture ofsodium borohydride (0.5 g, 0.013 mol) in anhydrous ethanol at 5° C.After 1 hour, 10% aqueous hydrochloric acid solution (35 ml) was addedslowly with copious gas evolution. The mixture was poured into water andwashed with diethyl ether. The organic phase was washed with saturatedsodium chloride solution, dried over magnesium sulfate, filtered andconcentrated under reduced pressure to provide the title compound as awhite solid, m.p. 118° C.

EXAMPLE 14 Preparation of3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-dimethoxy-4-trifluoromethylsulfinylpyrazole

The product of Example 4 (1.83 g, 0.0038 mol) was combined withmetachloroperbenzoic acid (80% weight, 0.9 g, 0.0042 mol) indichloromethane at 0° C. After 6 hours, the mixture was warmed to roomtemperature and stirred 11 hours. This was heated to reflux for 7 hourswhereupon more meta-chloroperbenzoic acid (80% weight, 0.9 g, 0.0042mol) was added and the reaction heated an additional 47 hours. Themixture was cooled to room temperature, poured into saturated aqueoussodium bicarbonate solution and washed with diethyl ether. The combinedorganic extracts were washed with saturated aqueous sodium bisulfitesolution and saturated aqueous sodium chloride solution. The organiclayer was dried over sodium sulfate, filtered and solvents removed underreduced pressure to leave an oil that was purified by silica gelchromatography using a hexanes:ethyl acetate mixture. The product (0.74g) was isolated as a solid, m.p. about 116° C. Also prepared by thismethod: Compounds 15, 19, and 20.

EXAMPLE 15 Preparation of3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(1-hydroxy-2,2,2-trifluoroethyl)-4-trifluoromethylthiopyrazole

The product of Example 3 (2.0 g, 0.0046 mol) was dissolved in anhydroustetrahydrofuran (10 mL). Trifluoromethyltrimethylsilane (0.8 mL, 0.0055mol) was added and the reaction cooled to 0° C.Tetrabutylammoniumfluoride (TBAF, 50 μL, cat.) was added. Afterintervals of 20 minutes, 1.5 hours, and 18 hours, aliquots of TBAF (50μL) were added at 0° C. followed by warming to room temperature. After21 hours, more trifluoromethyltrimethylsilane (0.8 mL, 0.0055 mol) wasadded and the reaction stirred for 5 days. This was poured into 10%hydrochloric acid (100 mL) and washed with diethyl ether (3×50 mL). Thecombined organic extracts were washed with saturated aqueous sodiumchloride solution, dried over magnesium sulfate, filtered and evaporatedto an oil. This was purified by silica gel chromatography using an ethylacetate in hexanes gradient to provide the title compound (1.08 g) as awhite solid, m.p. about 106° C.

The following representative test procedures, using compounds of theinvention, were conducted to determine the pesticidal use and activityof compounds of the invention against: a tick; certain insects,including aphids, caterpillars, a fly, a beetle larvae, a cockroach, aflea, two species of corn rootworm, a cutworm; and a nematode. Thespecific species tested were as follows:

    __________________________________________________________________________    GENUS, SPECIES  COMMON NAME                               ABBREVIATION    __________________________________________________________________________    Aphis nasturti  buckthorn aphid                               BA    Aphis gossypii  cotton aphid                               CA    Schizaphis graminum                    greenbug aphid                               GA    Spodoptera eridania                    southern armyworm                               SAW    Heliothis virescens                    tobacco budworm                               TBW    Musca domestica house fly  HF    Epilachna varivestis                    Mexican bean beetle                               MBB    Periplaneta americana                    American cockroach                               ACR    Rhipicephalus sanguineus                    dog tick   DT    Ctenocephalides felis                    cat flea   CF    Meloidogyne incognita                    southern root-knot                               SRKN                    nematode    Diabrotica virgifera virgifera                    western corn rootworm                               WCRW    Diabrotica undecimpunctata howardi                    southern corn rootworm                               SCRW    Agrotis ipsilon black cutworm                               BCW    __________________________________________________________________________

The test compounds were formulated for use according to the followingmethods.

For the tick, aphids, southern armyworm, tobacco budworm, house fly,Mexican bean beetle, American cockroach, cat flea, southern cornrootworm, western corn rootworm, black cutworm, and southern root-knotnematode, a solution or suspension was prepared by adding the testcompound to a solution of dimethylformamide, acetone, emulsifiers whichare alkylaryl polyether alcohols organic sulfonates, and water. Theresult was a 100 or 500 ppm concentration of the test compound.

For house fly tests, the water-acetone-DMF-emulsifier solution wasadjusted with a 20% by weight aqueous solution of sucrose to provide afinal 100 or 250 ppm concentration of the test compound.

For the western corn rootworm test, the water-acetone-DMF-emulsifiersolution was adjusted for a treatment rate of 0.15 or 0.5 ppm.

For southern corn rootworm and black cutworm tests, thewater-acetone-DMF-emulsifier solution was adjusted for a treatment rateof 2.5, 5, 6.75 or 10 ppm.

For cotton aphid systemic tests and black cutworm--systemic tests, thewateracetone-DMF-emulsifier solution was adjusted for a treatment rateof 10.0 ppm soil concentration.

For the greenbug aphid systemic test, the water-acetone-DMF-emulsifiersolution was adjusted for a treatment rate of 10 or 25 ppm soilconcentration.

For the southern root-knot nematode tests, thewater-acetone-DMF-emulsifier solution was adjusted for a treatment rateof 23 kg/ha soil concentration.

The above formulated test compounds were evaluated for their pesticidalactivity at specified concentrations, in ppm (parts per million) byweight or in kg/ha (kilograms per hectare). The following procedureswere used to evaluate a number of compounds within the scope of theinvention.

Buckthorn aphid (BA) or cotton aphid (CA): Adult and nymphal stages ofbuckthorn or cotton aphid were reared on potted dwarf nasturtium orcotton plants, respectively. Plants infested with 100-150 aphids werewet to runoff with the 100 or 500 ppm test compound formulation. As anuntreated control, a water-acetone-DMF-emulsifier solution containing notest compound was also applied to runoff to infested plants. The treatedplants were stored for one day for buckthorn aphid and three days forcotton aphid, after which the dead aphids were counted.

Southern armyworm (SAW), Mexican bean beetle (MBB): Bean leaves were wetto runoff with the 100 or 500 ppm test compound formulation. As anuntreated control, a water-acetone-DMF-emulsifier solution containing notest compound was also applied wet to runoff to bean leaves. Five or sixrandomly selected second instar southern armyworm larvae or Mexican beanbeetle larvae were introduced into each plastic container with the drytreated leaves. The container was closed and held for five days. Larvaewhich were unable to move the length of the body, even upon stimulationby prodding, were considered dead.

Tobacco budworm (TBW): Cotton leaves were wet to runoff with the 100 ppmtest compound formulation. As an untreated control, awater-acetone-DMF-emulsifier solution containing no test compound wasalso applied wet to runoff to cotton leaves. Ten randomly selectedsecond instar tobacco budworm larvae were introduced into plasticcontainers in which moist dental wicks and the dry treated leaves hadbeen placed. The cups were closed and held for five days. Larvae whichwere unable to move the length of the body, even upon stimulation byprodding, were considered dead.

House fly (HF): Four to six day old adult house flies were used. Theflies were immobilized by anesthetizing with carbon dioxide. A bait cupwas prepared which contained the 100 or 250 ppm test compoundformulation/sucrose solution and one or two absorbent cotton pad(s). Asan untreated control, a water-acetone-DMF-emulsifier-sucrose solutioncontaining no test compound was applied in a similar manner. The baitcup was introduced inside the cage prior to admitting 12-25 anesthetizedflies. Mortality was assessed after 24 hours.

American cockroach (ACR): Cat food or dog food pellets were added tojars containing 1-2 mls of the 500 ppm test formulation. As an untreatedcontrol, an aliquot of a water-acetone-DMF-emulsifier solutioncontaining no test compound was applied in a similar manner. After 48hours, roach nymphs were added to the jar. Contact and feeding mortalitywas assessed 1 and 5 days after infestation.

Cat flea (CF), dog tick (DT): Filter papers were treated with an aliquotof the 500 ppm test formulation. As an untreated control, an aliquot ofa water-acetone-DMF-emulsifier solution containing no test compound wasapplied in a similar manner. When dry, 2 treated filters were placed ina vial for the flea and another 2 filters in a vial for the tick. Fiveadult fleas were added to one vial and 5 adult ticks to the second vial.Contact mortality was assessed 1 day after infestation for the flea and14 days after infestation for the tick.

Southern root-knot nematode (SRKN): Eggs and second stage juveniles(J2s) of southern root-knot nematodes were obtained from infected rootsof reared tomato plants. Pots containing moist soil were treated withthe test compound solution for a treatment rate of 23 kg/ha. As anuntreated control, an aliquot of a water-acetone-DMF-emulsifier solutioncontaining no test compound was applied in a similar manner. Immediatelyafter treatment, eggs or J2s of southern root-knot nematode were addedto the treated soil. For tests with cotton, the seeds were placed on topof the soil the day of treatment and inoculation. For the tests withtomato, the seedlings were transplanted in the pot three days aftertreatment. The pots were kept in the greenhouse for 2-3 weeks. At thetermination of the test, roots of the tomato or cotton seedling wereevaluated for galling on a rating scale from 1 to 5 with one equal tosevere galling, relative to untreated control, and five to no galling,i.e., complete control.

Western corn rootworm (WCRW): The 500 ppm test formulation was appliedto dry sandy loam soil contained in a glass jar for a soil concentrationof 0.15 or 0.5 ppm. As an untreated control, an aliquot of awater-acetone-DMF-emulsifier solution containing no test compound wasapplied in a similar manner. After incubating covered for 24 hours, thesoil was mixed and four germinated corn seedlings were added to the jar.Ten neonate western corn rootworm larvae were placed in the jar. Sixdays after infestation, mortality was assessed by Berlese funnelextraction.

Southern corn rootworm (SCRW), Black cutworm (BCW): Corn seeds wereplaced in a glass jar and covered with dry sandy loam soil. The 500 ppmtest formulation was applied for a soil concentration of 2.5, 5, 6.75 or10 ppm. As an untreated control, an aliquot of awater-acetone-DMF-emulsifier solution containing no test compound wasapplied in a similar manner. After incubating covered for 24 hours, thesoil was mixed and inoculated with approximately 25 southern cornrootworm eggs. Following an additional 48 hours, two late second toearly third instar black cutworms were placed in the jar with a portionof insect diet. Eight days after infestation, mortality was assessedvisually for cutworm and by Berlese funnel extraction for rootworm.

Black cutworm--systemic test (BCW-Sys): Corn seeds were placed on top ofthe soil surface in pots containing moist soil. The test compoundsolution was applied as a drench to the top of the soil and seeds for atreatment rate equivalent to 10.0 ppm soil concentration. As anuntreated control, an aliquot of a water-acetone-DMF-emulsifier solutioncontaining no test compound was applied in a similar manner. The soilsurface and seeds were covered with moist soil. The pots were held inthe greenhouse for the duration of the bioassay. Ten days aftertreatment, the corn seedling was clipped and placed in a plastic cupwith 2 late second to early third instar black cutworm larvae. Mortalitywas assessed visually 4 days after infestation.

Greenbug aphid--systemic test (GA-Sys): Sorghum seeds were placed on topof the soil surface in pots containing moist soil. The rest compoundsolution was applied as a drench to the top of the soil and seeds for atreatment rate equivalent to 10 or 25 ppm soil concentration. As anuntreated control, an aliquot of a water-acetone-DMF-emulsifier solutioncontaining no test compound was applied in a similar manner. The soilsurface and seeds were covered with moist soil. The pots were held inthe greenhouse for the duration of the bioassay. When the sorghum seedsgerminated, greenbug aphids were sprinkled evenly over the sorghum potsto about 50 aphids per pot. The plants were rated for aphid control oneand three days after infestation.

Cotton aphid--systemic test (CA-Sys): Cotton seeds were placed on top ofthe soil surface in pots containing moist soil. The test compoundsolution was applied as a drench to the top of the soil and seeds for atreatment rate equivalent to 10.0 ppm soil concentration. As anuntreated control, an aliquot of a water-acetone-DMF-emulsifier solutioncontaining no test compound was applied in a similar manner. The soilsurface and seeds were covered with moist soil. The pots were held inthe greenhouse for the duration of the bioassay. When the cotyledons ofthe cotton were expanded (approximately 7 days after planting), thecotton was infested with approximately 25 cotton aphids (mixedpopulation). The plants were rated for aphid control three and six daysafter infestation.

The above procedures were used to evaluate a number of compounds withinthe scope of the invention. The following compounds in Table II wereactive against 1 or more insects described above up to 100% mortality.This activity is indicated by a

                                      TABLE II    __________________________________________________________________________    CPD                                     BCW-                                                GA-                                                   CA-    no.       BA         CA           SAW              TBW                 HF                   MBB                      ACR                         DT                           CF                             SRKN                                 WCRW                                     SCRW                                         BCW                                            Sys Sys                                                   Sys    __________________________________________________________________________     1 +   +  +  + +                 +     2     +     +               +   +     3        +  +                   +   +     4     +     +               +   +     5   +       +               +   +             +     6   + +     +               +   +     7     +     8                               +      +     9     +    10     +  +    +             +   +   +  +   +    11           +               +   +    12     +     +           +       +      +   +    13   + +  +  +    +      +   +   +    14   + +  +  +    +      +   +   +    15   + +     +    +      +   +   +    16     +  +  +    +          +   +    17           +    +          +   +             +    18     +     +    +  + +     +   +    19     +  +  +    +    +         +    20   + +     +    +    +                       +    21   + +  +  + +             +              +    __________________________________________________________________________

As is evident from the foregoing pesticidal uses, the present inventionprovides pesticidally active compounds and methods of use of saidcompounds for the control of a number of pest species which includes:arthropods, especially insects or mites; plant nematodes; or helminth orprotozoan pests. The compounds of formula (I) or pesticidally acceptablesalts thereof thus are advantageously employed in practical uses, forexample, in agricultural or horticultural crops, forestry, veterinarymedicine or livestock husbandry, or in public health. From this pointforward, whenever the term "compounds of formula (I)" is used this termembraces compounds of formula (I) and their pesticidally acceptablesalts. The term "compound of formula (I)" embraces a compound of formula(I) and a pesticidally acceptable salt thereof.

The present invention therefore provides a method of control of pests ata locus which comprises the treatment of the locus (e.g., by applicationor administration) with an effective amount of a compound of formula (I)or a pesticidally acceptable salt thereof, wherein the substituentgroups are as hereinbefore defined. The locus includes, for example, thepest itself or the place (plant, animal, person, field, structure,premises, forest, orchard, waterway, soil, plant or animal product, orthe like) where the pest resides or feeds.

The compounds of this invention are preferably used to control soilinsects, such as corn rootworm, termites (especially for protection ofstructures), root maggots, wireworms, root weevils, stalkborers,cutworms, root aphids, or grubs. They may also be used to provideactivity against plant pathogenic nematodes, such as root-knot, cyst,dagger, lesion, or stem or bulb nematodes, or against mites. For thecontrol of soil pests, for example corn rootworm, the compounds areadvantageously applied to or incorporated at an effective rate into thesoil in which crops are planted or to be planted or to the seeds orgrowing plant roots.

Furthermore, these compounds may be useful in the control via foliarapplication or systemic action of some arthropods, especially someinsects or mites, which feed on the above ground portions of plants.Control of foliar pests may additionally be provided by application tothe plant roots or plant seeds with subsequent systemic translocation tothe above ground portions of the plants.

In the area of public health, the compounds are especially useful in thecontrol of many insects, especially filth flies or other Dipteran pests,such as houseflies, stableflies, soldierflies, hornflies, deerflies,horseflies, midges, punkies, blackflies, or mosquitoes.

Compounds of the invention may be used in the following applications andon the following pests including arthropods, especially insects ormites, nematodes, or helminth or protozoan pests:

In the protection of stored products, for example cereals, includinggrain or flour, groundnuts, animal feedstuffs, timber or householdgoods, e.g. carpets and textiles, against attack by arthropods, moreespecially beetles, including weevils, moths or mites, for exampleEphestia spp. (flour moths), Anthrenus spp. (carpet beetles), Triboliumspp. (flour beetles), Sitophilus spp. (grain weevils) or Acarus spp.(mites).

In the control of cockroaches, ants or termites or similar arthropodpests in infested domestic or industrial premises or in the control ofmosquito larvae in waterways, wells, reservoirs or other running orstanding water.

For the treatment of foundations, structures or soil in the preventionof the attack on building by termites, for example, Reticulitermes spp.,Heterotermes spp., Coptotermes spp.

In agriculture against adults, larvae and eggs of Lepidoptera(butterflies and moths), e.g. Heliothis spp. such as Heliothis virescens(tobacco budworm), Heliothis artnigera and Heliothis zea, Spodopteraspp. such as S. exempta, S. frugiperda, S. exiqua, S. littoralis(Egyptian cotton worm), S. eridania (southern army worm), and Mamestraconfigurata (bertha army worm); Earias spp. e.g. E. insulana (Egyptianbollworm), Pectinophora spp. e.g. Pectinophora gossypiella (pinkbollworm), Ostrinia spp. such as O. nubilalis (European cornborer),Trichoplusia ni (cabbage looper), Artogeia spp. (cabbage worms),Laphygna spp. (army worms), Agrotis and Amathes spp. (cutworms), Wiseanaspp. (porina moth), Chilo spp. (rice stem borer), Tryporyza spp. andDiatraea spp. (sugar cane borers and rice borers), Sparganothispilleriana (grape berry moth), Cydia pomonella (codling moth), Archipsspp. (fruit tree tortrix moth), Plutella xylostella (diamond back moth),Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella,Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria,Euproctis chrysorrhoea, Lymantria spp. Bucculatrix thurberiella,Phyllocnistis citrella, Euxoa spp., Feltia brassicae, Panolis flammea,Prodenia litura, Carpocapsa pomonelia, Pyrausta nubilalis, Ephestiakuehniella, Galleria mellonella, Tineola bisselliella, Tineapellionella, Hofmannophila pseudospretella, Cacoecia podana Capusreticulana, Choristoneura fumiferana, Clysia ambiguellis, Homonamagnanime and Tortix viridana.

Against adults and larvae of Coleoptera (beetles) e.g. Hypothenemushampei (coffee berry borer), Hylesinus spp. (bark beetles), Anthonomusspp. e.g. grandis (cotton boll weevil), Acalymma spp. (cucumberbeetles), Lema spp., Psylliodes spp., Leptinotarsa decemlineata(Colorado potato beetle), Diabrotica spp. (corn rootworms), Gonocephalumspp. (false wire worms), Agriotes spp., Limonius spp. (wireworms),Dermolepida spp., Popillia spp., Heteronychus spp. (white grubs),Phaedon cochleariae (mustard beetle), Epitrix spp. (flea beetles),Lissorhoptrus oryzophilus (rice water weevil), Meligethes spp. (pollenbeetles), Ceutorhynchus spp., Rhynchophorus and Cosmopolites spp. (rootweevils), Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus,Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni,Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp.,Oryzaephilus surinamensis, Sitophilus spp., Otiorrhynchus sulcatus,Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica,Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctusspp., Maligethes aeneus, Ptinus spp., Niptus hololeucrus, Gibbiumpsylloides, Tribolium spp., Tenebrio molitor, Conoderus spp., Melolonthamelolontha, Amphimallon solstitialis and Costelytra zealandica.

Against Heteroptera (Hemiptera and Homoptera) e.g. Psylla spp., Bemisiaspp., Trialeurodes spp., Aphis spp., Myzus spp., Megoura viciae,Phylloxera spp., Adelges spp., Phorodon humuli (hop damson aphid),Aeneolamia spp., Nephotettix spp. (rice leaf hoppers), Enpoasca spp.,Nilaparvata spp., Perkinsiella spp., Pyrilla spp., Aonidiella spp. (redscales), Coccus spp., Pseucoccus spp., Helopeltis spp. (mosquito bugs),Lygus spp., Dysdercus spp., Oxycarenus spp., Nezara spp., Eurygasterspp., Piesma quadrata, Cimex lectulanus, Rhodnius prolixus and Triatomaspp. Aspidiotus hederae, Aeurodes brassicae, Brevicoryne brassicae,Cryptomyzus ribis, Doralis fabae, Doralis pomi., Eriosoma lanigerum,Hyalopterus arundinis, Macrosiphum avenae, Phorodon humuli,Rhopalosiphum padi, Euscelis bilobatus, Nephotettix cincticeps, Lecaniumcorni, Saissetia oleae, Laodelphax stratellus.

Against Hymenoptera e.g. Athalia spp. and Cephus spp. (saw flies), Attaspp. (leaf cutting ants), Diprion spp., Hopolocampa spp., Lasius spp.,Monomorium spp., Polistes spp., Vespa spp., Vespula spp., and Solenopsisspp.

Against Diptera e.g. Delia spp. (root maggots), Atherigona spp. andChlorops spp., Sarcophaga spp., Musca spp., Phormia spp., Aedes spp.,Anopheles spp., Simulium spp., (shoot flies), Phytomyza spp. (leafminers), Ceratitis spp. (fruit flies). Culex spp., Drosophilamelanogaster, Ceratitis capitata, Dacus oleae, Tipula paludosa,Calliphora erythrocephala, Lucilia spp., Chrysomyia spp. Cuterebra spp.Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Fannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyani.

Against Thysanoptera such as Thrips tabaci, Hercinothrips femoralis, andFrankliniella spp.

Against Orthoptera such as Locusta and Schistocerca spp. (locusts andcrickets), e.g. Gryllus spp., and Acheta spp. for example, Blattaorientalis, Periplaneta americana, Leucophaea maderae, Blatellagermanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoriamigratorioides, Melanoplus differentialis and Schistocerca gregaria.

Against Collembola e.g. Sminthurus spp. and Onychiurus spp.(springtails); Periplaneta spp. and Blattela spp. (roaches).

Against Isoptera e.g. Odontotermes spp., Reticuletermes spp.,Coptotermes spp. (termites).

Against Dermaptera e.g. Forticula sp. (earwigs).

Against arthropods of agricultural significance such as Acari (mites)e.g. Tetranychus spp., Panonychus spp., Bryobia spp. (spider mites),Ornithonyssus spp. (fowl mites), Eriophyes spp. (gall mites), andPolyphadotarsonemus spp.

Against Thysanura, for example Lepisma saccharia.

Against Anoplura for example, Phylloxera vastatrix, Pemphigus spp.,Pediculus humanus corporis, Haemzatopinus spp. and Linognathus spp.

Against Mallophaga, for example, Trichodectes spp. and Damalinea spp.

Against Siphonoptera, for example, Xenopsylla cheopis and Ceratophyllusspp.

Against other arthopods, such as Blaniulus spp. (millipedes),Scutigerella spp. (symphilids), Oniscus spp. (woodlice) and Trops spp.(crustacea).

Against Isopoda, for example, Oniseus asellus, Armadillidium vulgare andPorcellio scaber.

Against Chilopoda, for example, Geophilus carpophagus and Scutigeraspex.

Against nematodes which attack plants or trees of importance toagriculture, forestry or horticulture either directly or by spreadingbacterial, viral, mycoplasma or fungal diseases of the plants, forexample, root-knot nematodes such as Meloidogyne spp. (e.g. M.incognita); cyst nematodes such as Globodera spp. (e.g. G.rostochiensis); Heterodera spp. (e.g. H. avenae); Radopholus spp. (e.g.R. similis); lesion nematodes such as Pratylenchus spp. (e.g. P.pratensis); Belonolaimus spp. (e.g. B. gracilis); Tylenchulus spp. (e.g.T. semipenetrans); Rotylenchulus spp. (e.g. R. reniformis); Rotylenchusspp. (R. robustus); Helicotylenchus spp. (e.g. H. multicinctus);Hemicycliophora spp. (e.g. H. gracilis); Criconemoides spp. (e.g. C.similis); Trichodorus spp. (e.g. T. primitivus); dagger nematodes suchas Xiphinema spp. (e.g. X. diversicaudatum), Longidorus spp. (e.g. L.elongatus); Hoplolaimus spp. (e.g. H. coronatus); Aphelenchoides spp.(e.g. A. ritzema-bosi, A. besseyi); stem and bulb eelworm such asDitylenchus spp. (e.g. D. dipsacai).

In the field of veterinary medicine or livestock husbandry or in themaintenance of public health against arthropods, helminths or protozoawhich are parasitic internally or externally upon vertebrates,particularly warm-blooded vertebrates, for example man or domesticanimals, e.g. cattle, sheep, goats, equines, swine, poultry, dogs orcats, for example Acarina, including ticks (e.g. Ixodes spp., Boophilusspp. e.g. Boophilus microplus, Amblyomma spp., Hyalomma spp.,Rhipicephalus spp., e.g. Rhipicephalus appendiculatus, Haemaphysalisspp., Dermacentor spp., Omithodorus spp. (e.g. Ornithodorus moubata))and mites (e.g. Damalinia spp., Dernahyssus gallinae, Sarcoptes spp.,e.g. Sarcoptes scabiei, Psoroptes spp., Chorioptes spp., Demodex spp.,Eutrombicula spp.); Diptera (e.g. Aedes spp., Anopheles spp., Muscaspp., Hypoderma spp., Gasterophilus spp., Simulium spp); Hemiptera (e.g.Triatoma spp); Phthirapter (e.g. Damalinia spp., Linognathus spp.);Siphonaptera (e.g. Ctenocephalides spp.); Dictyoptera (e.g. Periplanetaspp., Blatella spp.); Hymenoptera (e.g. Monomorium pharaonis); forexample against infections of the gastro-intestinal tract caused byparasitic nematode worms, for example members of the familyTrichostrongylidae, Nippostrongylus brasiliensis, Trichinella spiralis,Haemonchus contortus, Trichostrongylus colubriformis, Nematodirus batus,Osterragis circumcincta, Trichostrongylus axei, Cooperia spp. andHymenolepis nana; in the control and treatment of protozoal diseasescaused by, for example, Eimeria spp. e.g. Eimeria tenella, Eimeriaacervulina, Eimeria brunetti, Eimeria maxima and Eimeria necatrix,Trypanosoms cruzi, Leishaminia spp., Plasmodium spp., Babesis spp.,Trichomonadidae spp., Histomanas spp., Giardia spp., Toxoplasma spp.,Entamoeba histolytica and Theileria spp.

In practical use for the control of arthropods, especially insects ormites, or nematode pests of plants, a method, for example, comprisesapplying to the plants or to the medium in which they grow an effectiveamount of a compound of the invention. For such a method, the activecompound is generally applied to the locus in which the arthropod ornematode infestation is to be controlled at an effective rate in therange of about 0.005 kg to about 15 kg of the active compound perhectare of locus treated. Under ideal conditions, depending on the pestto be controlled, a lower rate may offer adequate protection. On theother hand, adverse weather conditions, resistance of the pest or otherfactors may require that the active ingredient be used at higher rates.The optimum rate depends usually upon a number of factors, for example,the type of pest being controlled, the type or the growth stage of theinfested plant, the row spacing or also the method of application. Morepreferably an effective rate range of the active compound is from about0.01 kg/ha to about 2 kg/ha.

When a pest is soil-borne, the active compound, generally in aformulated composition, is distributed evenly over the area to betreated (i.e., for example broadcast or band treatment) in anyconvenient manner. Application may be made, if desired, to the field orcrop-growing area generally or in close proximity to the seed or plantto be protected from attack. The active component can be washed into thesoil by spraying with water over the area or can be left to the naturalaction of rainfall. During or after application, the formulated compoundcan, if desired, be distributed mechanically in the soil, for example byploughing, disling, or use of drag chains. Application can be prior toplanting, at planting, after planting but before sprouting has takenplace, or after sprouting. Additionally, a method of control may alsocomprise treatment of the seed prior to planting with subsequent controleffected after planting the seed.

Methods of control of pests also comprise application to or treatment ofthe foliage of plants to control arthropods, especially insects ormites, or nematodes attacking the aerial parts of the plants. Inaddition, methods of control of pests by the invention compounds areprovided to control pests which feed on parts of the plant remote fromthe point of application, e.g., leaf feeding insects which arecontrolled via systemic action of the active compound when applied forexample to the roots of a plant or to the plant seed prior to planting.Furthermore, the compounds of the invention may reduce attacks on aplant by means of antifeeding or repellent effects.

The compounds of the invention and methods of control of pests therewithare of particular value in the protection of field, forage, plantation,glasshouse, orchard or vineyard crops, of ornamentals, or of plantationor forest trees, for example: cereals (such as maize, wheat, rice, orsorghum), cotton, tobacco, vegetables (such as beans, cole crops,curcurbits, lettuce, onions, tomatoes or peppers), field crops (such aspotatoes, sugar beets, ground nuts, soybeans, or oil seed rape), sugarcane, grassland or forage crops (such as maize, sorghum, or lucerne),plantations (such as tea, coffee, cocoa, banana, palm oil, coconut,rubber, or spices), orchards or groves (such as of stone or pit fruit,citrus, kiwifruit, avocado, mango, olives or walnuts), vineyards,ornamental plants, flowers or vegetables or shrubs under glass or ingardens or parks, or forest trees (both deciduous and evergreen) inforests, plantations or nurseries.

They are also valuable in the protection of timber (standing, felled,converted, stored or structural) from attack, for example, by sawfliesor beetles or termites.

They have applications in the protection of stored products such asgrains, fruits, nuts, spices or tobacco, whether whole, milled orcompounded into products, from moth, beetle, mite or grain weevilattack. Also protected are stored animal products such as skins, hair,wool or feathers in natural or converted form (e.g. as carpets ortextiles) from moth or beetle attack as well as stored meat, fish orgrains from beetle, mite or fly attack.

Additionally, the compounds of the invention and methods of use thereofare of particular value in the control of arthropods, helminths orprotozoa which are injurious to, or spread or act as vectors of diseasesin man and domestic animals, for example those hereinbefore mentioned,and more especially in the control of ticks, mites, lice, fleas, midges,or biting, nuisance or myiasis flies. The compounds of the invention areparticularly useful in controlling arthropods, helminths or protozoawhich are present inside domestic host animals or which feed in or onthe skin or suck the blood of the animal, for which purpose they may beadministered orally, parenterally, percutaneously or topically.

Furthermore, compounds of the invention may be useful for coccidiosis, adisease caused by infections from protozoan parasites of the genusEimeria. It is an important potential cause of economic loss in domesticanimals and birds, particularly those raised or kept under intensiveconditions. For example, cattle, sheep, pigs or rabbits may be affected,but the disease is especially important in poultry, particularly inchickens. Administration of a small amount of a compound of theinvention, preferably by a combination with feed is effective inpreventing or greatly reducing the incidence of coccidiosis. Thecompounds are effective against both the cecal form and the intestinalforms. Furthermore, the compounds of the invention may also exert aninhibiting effect on oocytes by greatly reducing the number andsporulation of those produced. The poultry disease is generally spreadby the birds picking up the infectious organism in droppings in or oncontaminated litter, ground, food, or drinking water. The disease ismanifested by hemorrhage, accumulation of blood in the ceca, passage ofblood to the droppings, weakness and digestive disturbances. The diseaseoften terminates in the death of the animal, but the fowl which survivesevere infections have had their market value substantially reduced as aresult of the infection.

The compositions hereinafter described for application to growing cropsor crop growing loci or as a seed dressing may, in general,alternatively be employed for topical application to man or animals orin the protection of stored products, household goods, property or areasof the general environment. Suitable means of applying the compounds ofthe invention include:

to growing crops as foliar sprays, dusts, granules, fogs or foams oralso as suspensions of fmely divided or encapsulated compositions assoil or root treannents by liquid drenches, dusts, granules, smokes orfoams; to seeds of crops via application as seed dressings by liquidslurries or dusts;

to persons or animals infested by or exposed to infestation byarthropods, helminths or protozoa, by parenteral, oral or topicalapplication of compositions in which the active ingredient exhibits animmediate and/or prolonged action over a period of time against thearthropods, helminths or protozoa, for example by incorporation in feedor suitable orally-ingestible pharmaceutical formulations, edible baits,salt licks, dietary supplements, pour-on formulations, sprays, baths,dips, showers, jets, dusts, greases, shampoos; creams, wax smears orlivestock selftreatment systems;

to the environment in general or to specific locations where pests maylurk, including stored products, timber, household goods, or domestic orindustrial premises, as sprays, fogs, dusts, smokes, wax-smears,lacquers, granules or baits, or in tricklefeeds to waterways, wells,reservoirs or other rnnng or standing water;

to domestic animals in feed to control fly larvae feeding in theirfeces.

In practice, the compounds of the invention most frequently form partsof compositions. These compositions can be employed to control:arthopods, especially insects or mites; nematodes; or helminth orprotozoan pests. The compositions may be of any type known in the artsuitable for application to the desired pest in any premises or indooror outdoor area or by internal or external administration tovertebrates. These compositions contain at least one compound of formula(I) or a pesticidally acceptable salt thereof, such as describedearlier, as the active ingredient in combination or association with oneor more other compatible components which are for example, solid orliquid carriers or diluents, adjuvants, surface-active agents, or thelike appropriate for the intended use and which are agronomically ormedicinally acceptable. These compositions, which may be prepared by anymanner known in the art, likewise form a part of this invention.

These compositions may also contain other kinds of ingredients such asprotective colloids, adhesives, thickeners, thixotropic agents,penetrating agents, spray oils (especially for acaridical use),stabilizers, preservative agents (especially mold preservatives),sequestering agents, or the like, as well as other known activeingredients with pesticidal properties (particularly insecticidal,miticidal, nematicidal, or fungicidal) or with properties regulating thegrowth of plants. More generally, the compounds employed in theinvention may be combined with all the solid or liquid additivescorresponding to the usual techniques of formulation.

Compositions suitable for applications in agriculture, horticulture, orthe like include formulations suitable for use as, for example, sprays,dusts, granules, fogs, foams, emulsions, or the like.

Compositions suitable for administration to vertebrates or man includepreparations suitable for oral, parenteral, percutaneous, e.g. pour-on,or topical administration.

Compositions for oral administration comprise one or more of thecompounds of formula (I), or pesticidally acceptable salts thereof inassociation with pharmaceutically acceptable carriers or coatings andinclude, for example, tablets, pills, capsules, pastes, gels, drenches,medicated feeds, medicated drinking water, medicated dietarysupplements, slow-release boluses or other slow-release devices intendedto be retained within the gastrointestinal tract. Any of these mayincorporate the active ingredient contained within microcapsules orcoated with acid-labile or alkali-labile or other pharmaceuticallyacceptable enteric coatings. Feed premixes or concentrates containingcompounds of the present invention for use in preparation of medicateddiets, drinking water or other materials for consumption by animals mayalso be used.

Compositions for parenteral administration include solutions, emulsionsor suspensions in any suitable pharmaceutically acceptable vehicle, orsolid or semisolid subcutaneous implants or pellets designed to releasethe active ingredient over a protracted period of time and may beprepared and made sterile in any appropriate manner known to the art.

Compositions for percutaneous and topical administration include sprays,dusts, baths, dips, showers, jets, greases, shampoos, creams,wax-smears, or pour-on preparations or devices (e.g. ear tags attachedexternally to animals in such a way as to provide local or systemicarthropod control).

Solid or liquid baits, suitable for controlling arthropods, comprise oneor more compounds of formula (I), or pesticidally acceptable saltsthereof, and a carrier or diluent which may include a food substance orsome other substance to induce consumption by the arthropod.

The effective use doses of the compounds employed in the invention canvary within wide limits, particularly depending on the nature of thepest to be eliminated or degree of infestation, for example, of cropswith these pests. In general, the compositions according to theinvention usually contain about 0.05 to about 95% (by weight) of one ormore active ingredients according to the invention, about 1 to about 95%of one or more solid or liquid carriers and, optionally, about 0.1 toabout 50% of one or more other compatible components, such assurface-active agents or the like.

In the present account, the term "carrier" denotes an organic orinorganic ingredient, natural or synthetic, with which the activeingredient is combined to facilitate its application, for example, tothe plant, to seeds or to the soil. This carrier is therefore generallyinert and it must be acceptable (for example, agronomically acceptable,particularly to the treated plant).

The carrier may be a solid, for example, clays, natural or syntheticsilicates, silica, resins, waxes, solid fertilizers (for exampleammonium salts), ground natural minerals, such as kaolins, clays, talc,chalk, quartz, attapulgite, montmorillonite, bentonite or diatomaceousearth, or ground synthetic minerals, such as silica, alumina, orsilicates especially aluminum or magnesium silicates. As solid carriersfor granules the following are suitable: crushed or fractionated naturalrocks such as calcite, marble, pumice, sepiolite and dolomite; syntheticgranules of inorganic or organic meals; granules of organic materialsuch as sawdust, coconut shells, corn cobs, corn husks or tobaccostalks; kieselguhr, tricalcium phosphate, powdered cork, or absorbentcarbon black; water soluble polymers, resins, waxes; or solidfertilizers. Such solid compositions may, if desired, contain one ormore compatible wetting, dispersing, emulsifying or coloring agentswhich, when solid, may also serve as a diluent.

The carrier may also be liquid, for example: water; alcohols,particularly butanol or glycol, as well as their ethers or esters,particularly methylglycol acetate; ketones, particularly acetone,cyclohexanone, methylethylketone, methylisobutylketone, or isophorone;petroleum fractions such as paraffinic or aromatic hydrocarbons,particularly xylenes or alkyl naphthalenes; mineral or vegetable oils;aliphatic chlorinated hydrocarbons, particularly trichloroethane ormethylene chloride; aromatic chlorinated hydrocarbons, particularlychlorobenzenes; water-soluble or strongly polar solvents such asdimethylformamide, dimethyl sulfoxide, or N-methylpyrrolidone; liquefiedgases; or the like or a mixture thereof.

The surface-active agent may be an emulsifying agent, dispersing agentor wetting agent of the ionic or non-ionic type or a mixture of suchsurface-active agents. Amongst these are e.g., salts of polyacrylicacids, salts of lignosulfonic acids, salts of phenolsulfonic ornaphthalenesulfonic acids, polycondensates of ethylene oxide with fattyalcohols or fatty acids or fatty esters or fatty amines, substitutedphenols (particularly alkylphenols or arylphenols), salts ofsulfosuccinic acid esters, taurine derivatives (particularlyalkyltaurates), phosphoric esters of alcohols or of polycondensates ofethylene oxide with phenols, esters of fatty acids with polyols, orsulfate, sulfonate or phosphate functional derivatives of the abovecompounds. The presence of at least one surface-active agent isgenerally essential when the active ingredient and/or the inert carrierare only slightly water soluble or are not water soluble and the carrieragent of the composition for application is water.

Compositions of the invention may further contain other additives suchas adhesives or colorants. Adhesives such as carboxymethylcellulose ornatural or synthetic polymers in the form of powders, granules orlattices, such as arabic gum, polyvinyl alcohol or polyvinyl acetate,natural phospholipids, such as cephalins or lecithins, or syntheticphospholipids can be used in the formulations. It is possible to usecolorants such as inorganic pigments, for example: iron oxides, titaniumoxides or Prussian Blue; organic dyestuffs, such as alizarin dyestuffs,azo dyestuffs or metal phthalocyanine dyestuffs; or trace nutrients suchas salts of iron, manganese, boron, copper, cobalt, molybdenum or zinc.

Compositions containing compounds of formula (I), or pesticidallyacceptable salts thereof, which may be applied to control arthropod,plant nematode, helminth or protozoan pests, may also contain synergists(e.g. piperonyl butoxide or sesamex), stabilizing substances, otherinsecticides, acaricides, plant nematocides, anthelmintics oranticoccidials, fungicides (agricultural or veterinary as appropriate,e.g. benomyl and iprodione), bactericides, arthropod or vertebrateattractants or repellents or pheromones, deodorants, flavoring agents,dyes, or auxiliary therapeutic agents, e.g. trace elements. These may bedesigned to improve potency, persistence, safety, uptake where desired,spectrum of pests controlled or to enable the composition to performother useful functions in the same animal or area treated.

Examples of other pesticidally-active compounds which may be includedin, or used in conjunction with the compositions of the presentinvention are: acephate, chlorpyrifos, demeton-S-methyl, disulfoton,ethoprofos, fenitrothion, fenarniphos, fonofos, isazophos, isofenphos,malathion, monocrotophos, parathion, phorate, phosalone,pirimiphos-methyl, terbufos, triazophos, cyflututhrin, cypermethrin,deltamethrin, fenpropathrin, fenvalerate, permethrin, tefluthrin,aldicarb, carbosulfan, methomyl, oxamyl, pirimicarb, bendiocarb,teflubenzuron, dicofol, endosulfan, lindane, benzoximate, cartap,cyhexatin, tetradifon, avermectins, ivermectins, milbemycins,thiophanate, trichlorfon, dichlorvos, diaveridine or dimetriadazole.

For their agricultural application, the compounds of the formula (I), orpesticidally acceptable salts thereof, are therefore generally in theform of compositions, which are in various solid or liquid forms.

Solid forms of compositions which can be used are dusting powders (witha content of the compound of formula (I), or a pesticidally acceptablesalt thereof, ranging up to 80%), wettable powders or granules(including water dispersible granules), particularly those obtained byextrusion, compacting, impregnation of a granular carrier, orgranulation starting from a powder (the content of the compound offormula (I), or a pesticidally acceptable salt thereof, in thesewettable powders or granules being between about 0.5 and about 80%).Solid homogeneous or heterogeneous compositions containing one or morecompounds of formula (I), or pesticidally acceptable salts thereof, forexample granules, pellets, briquettes or capsules, may be used to treatstanding or running water over a period of time. A similar effect may beachieved using trickle or intermittent feeds of water dispersibleconcentrates as described herein.

Liquid compositions, for example, include aqueous or non-aqueoussolutions or suspensions (such as emulsifiable concentrates, emulsions,flowables, dispersions, or solutions) or aerosols. Liquid compositionsalso include, in particular, emulsifiable concentrates, dispersions,emulsions, flowables, aerosols, wettable powders (or powder forspraying), dry flowables or pastes as forms of compositions which areliquid or intended to form liquid compositions when applied, for exampleas aqueous sprays (including low and ultra-low volume) or as fogs oraerosols.

Liquid compositions, for example, in the form of emulsifiable or solubleconcentrates most frequently comprise about 5 to about 80% by weight ofthe active ingredient, while the emulsions or solutions which are readyfor application contain, in their case, about 0.01 to about 20% of theactive ingredient. Besides the solvent, the emulsifiable or solubleconcentrates may contain, when required, about 2 to about 50% ofsuitable additives, such as stabilizers, surface-active agents,penetrating agents, corrosion inhibitors, colorants or adhesives.Emulsions of any required concentration, which are particularly suitablefor application, for example, to plants, may be obtained from theseconcentrates by dilution with water. These compositions are includedwithin the scope of the compositions which may be employed in thepresent invention. The emulsions may be in the form of water-in-oil oroil-in-water type and they may have a thick consistency.

The liquid compositions of this invention may, in addition to normalagricultural use applications, be used for example to treat substratesor sites infested or liable to infestation by arthropods (or other pestscontrolled by compounds of this invention) including premises, outdooror indoor storage or processing areas, containers or equipment orstanding or running water.

All these aqueous dispersions or emulsions or spraying mixtures can beapplied, for example, to crops by any suitable means, chiefly byspraying, at rates which are generally of the order of about 100 toabout 1,200 liters of spraying mixture per hectare, but may be higher orlower (e.g. low or ultra-low volume) depending upon the need orapplication technique. The compounds or compositions according to theinvention are conveniently applied to vegetation and in particular toroots or leaves having pests to be elimnated. Another method ofapplication of the compounds or compositions according to the inventionis by chemigation, that is to say, the addition of a formulationcontaining the active ingredient to irrigation water. This irrigationmay be sprinkler irrigation for foliar pesticides or it can be groundirrigation or underground irrigation for soil or for systemicpesticides.

The concentrated suspensions, which can be applied by spraying, areprepared so as to produce a stable fluid product which does not settle(fine grinding) and usually contain from about 10 to about 75% by weightof active ingredient, from about 0.5 to about 30% of surface-activeagents, from about 0.1 to about 10% of thixotropic agents, from about 0to about 30% of suitable additives, such as antifoaming agents,corrosion inhibitors, stabilizers, penetrating agents, adhesives and, asthe carrier, water or an organic liquid in which the active ingredientis poorly soluble or insoluble. Some organic solids or inorganic saltsmay be dissolved in the carrier to help prevent settling or asantifreezes for water.

The wettable powders (or powder for spraying) are usually prepared sothat they contain from about 10 to about 80% by weight of activeingredient, from about 20 to about 90% of a solid carrier, from about 0to about 5% of a wetting agent, from about 3 to about 10% of adispersing agent and, when necessary, from about 0 to about 80% of oneor more stabilizers and/or other additives, such as penetrating agents,adhesives, anti-caking agents, colorants, or the like. To obtain thesewettable powders, the active ingredient(s) is(are) thoroughly mixed in asuitable blender with additional substances which may be impregnated onthe porous filler and is(are) ground using a mill or other suitablegrinder. This produces wettable powders, the wettability and thesuspendability of which are advantageous. They may be suspended in waterto give any desired concentration and this suspension can be employedvery advantageously in particular for application to plant foliage.

The "water dispersible granules (WG)" (granules which are readilydispersible in water) have compositions which are substantially close tothat of the wettable powders. They may be prepared by granulation offormulations described for the wettable powders, either by a wet route(contacting finely divided active ingredient with the inert filler and alittle water, e.g. 1 to 20% by weight, or with an aqueous solution of adispersing agent or binder, followed by drying and screening), or by adry route (compacting followed by grinding and screening).

The application dose (effective dose) of active ingredient, also as aformulated composition, is generally between about 0.005 and about 15kg/ha, preferably between about 0.01 and about 2 kg/ha. Therefore, therates and concentrations of the formulated compositions may varyaccording to the method of application or the nature of the compositionsor use thereof. Generally speaking, the compositions for application tocontrol arthropod, plant nematode, helminth or protozoan pests usuallycontain from about 0.00001% to about 95%, more particularly from about0.0005% to about 50% by weight of one or more compounds of formula (I),or pesticidally acceptable salts thereof, or of total active ingredients(that is to say the compound of formula (I), or a pesticidallyacceptable salt thereof, together with: other substances toxic toarthropods or plant nematodes, anthelmintics, anticoccidials,synergists, trace elements or stabilizers). The actual compositionsemployed and their rate of application will be selected to achieve thedesired effect(s) by the farmer, livestock producer, medical orveterinary practitioner, pest control operator or other person skilledin the art.

Solid or liquid compositions for application topically to animals,timber, stored products or household goods usually contain from about0.00005% to about 90%, more particularly from about 0.001% to about 10%,by weight of one or more compounds of formula (I) or pesticidallyacceptable salts thereof. For administration to animals orally orparenterally, including percutaneously solid or liquid compositions,these normally contain from about 0.1% to about 90% by weight of one ormore compounds of formula (I) or pesticidally acceptable salts thereof.Medicated feedstuffs normally contain from about 0.001% to about 3% byweight of one or more compounds of formula (I) or pesticidallyacceptable salts thereof. Concentrates or supplements for mixing withfeedstuffs normally contain from about 5% to about 90%, preferably fromabout 5% to about 50%, by weight of one or more compounds of formula (I)or pesticidally acceptable salts thereof. Mineral salt licks normallycontain from about 0.1% to about 10% by weight of one or more compoundsof formula (I) or pesticidally acceptable salts thereof.

Dusts or liquid compositions for application to livestock, persons,goods, premises or outdoor areas may contain from about 0.0001% to about15%, more especially from about 0.005% to about 2.0%, by weight, of oneor more compounds of formula (I) or pesticidally acceptable saltsthereof. Suitable concentrations in treated waters are between about0.0001 ppm and about 20 ppm, more particularly about 0.001 ppm to about5.0 ppm of one or more compounds of formula (I), or pesticidallyacceptable salts thereof, and may be used therapeutically in fishfarming with appropriate exposure times. Edible baits may contain fromabout 0.01% to about 5%, preferably from about 0.01% to about 1.0%, byweight, of one or more compounds of formula (I) or pesticidallyacceptable salts thereof.

When administered to vertebrates parenterally, orally or by percutaneousor other means, the dosage of compounds of formula (I), or pesticidallyacceptable salts thereof, will depend upon the species, age, and healthof the vertebrate and upon the nature and degree of its actual orpotential infestation by arthropod, helminth or protozoan pests. Asingle dose of about 0.1 to about 100 mg, preferably about 2.0 to about20.0 mg, per kg body weight of the animal or doses of about 0.01 toabout 20.0 mg, preferably about 0.1 to about 5.0 mg, per kg body weightof the animal per day, for sustained medication, are generally suitableby oral or parenteral administration. By use of sustained releaseformulations or devices, the daily doses required over a period ofmonths may be combined and administered to animals on a single occasion.

The following composition EXAMPLES 16-A-16-L illustrate compositions foruse against arthropods, especially mites or insects, plant nematodes, orhelminth or protozoan pests which comprise, as active ingredient,compounds of formula (I), or pesticidally acceptable salts thereof, suchas those described in the preparative examples. The compositionsdescribed in EXAMPLES 16-A-16-L can each be diluted to give a sprayablecomposition at concentrations suitable for use in the field. Genericchemical descriptions of the ingredients (for which all of the followingpercentages are in weight percent), used in the composition EXAMPLES16-A-16-L exemplified below, are as follows:

    ______________________________________    Trade Name Chemical Description    ______________________________________    Ethylan BCP               Nonylphenol ethylene oxide condensate    Soprophor BSU               Tristyrylphenol ethylene oxide condensate    Arylan CA  A 70% w/v solution of calcium dodecylbenzene-               sulfonate    Solvesso 150               Light C.sub.10 aromatic solvent    Arylan S   Sodium dodecylbenzenesulfonate    Darvan No 2               Sodium lignosulfonate    Celite PF  Synthetic magnesium silicate carrier    Sopropon T36               Sodium salts of polycarboxylic acids    Rhodigel 23               Polysaccharide xanthan gum    Bentone 38 Organic derivative of magnesium montmorillonite    Aerosil    Microfine silicon dioxide    ______________________________________

EXAMPLE 16-A

A water soluble concentrate is prepared with the composition as follows:

    ______________________________________    Active ingredient  7%    Ethylan BCP       10%    N-methylpyrrolidone                      83%    ______________________________________

To a solution of Ethylan BCP dissolved in a portion ofN-methylpyrrolidone is added the active ingredient with heating andstirring until dissolved. The resulting solution is made up to volumewith the remainder of the solvent.

EXAMPLE 16-B

An emulsifiable concentrate (EC) is prepared with the composition asfollows:

    ______________________________________    Active ingredient  7%    Soprophor BSU      4%    Arylan CA          4%    N-methylpyrrolidone                      50%    Solvesso 150      35%    ______________________________________

The first three components are dissolved in N-methylpyrrolidone and tothis is then added the Solvesso 150 to give the final volume.

EXAMPLE 16-C

A wettable powder (WP) is prepared with the composition as follows:

    ______________________________________           Active ingredient                     40%           Arylan S   2%           Darvan No 2                      5%           Celite PF 53%    ______________________________________

The ingredients are mixed and ground in a hammer-mill to a powder with aparticle size of less than 50 microns.

EXAMPLE 16-D

An aqueous-flowable formulation is prepared with the composition asfollows:

    ______________________________________    Active ingredient                    40.00%    Ethylan BCP     1.00%    Sopropon T360   0.20%    Ethylene glycol 5.00%    Rhodigel 230    0.15%    Water           53.65%    ______________________________________

The ingredients are intimately mixed and are ground in a bead mill untila mean particle size of less than 3 microns is obtained.

EXAMPLE 16-E

An emulsifiable suspension concentrate is prepared with the compositionas follows:

    ______________________________________    Active ingredient                    30.0%    Ethylan BCP     10.0%    Bentone 38      0.5%    Solvesso 150    59.5%    ______________________________________

The ingredients are intimately mixed and ground in a beadmill until amean particle size of less than 3 microns is obtained.

EXAMPLE 16-F

A water dispersible granule is prepared with the composition as follows:

    ______________________________________           Active ingredient                     30%           Darvan No 2                     15%           Arylan S   8%           Celite PF 47%    ______________________________________

The ingredients are mixed, micronized in a fluid-energy mill and thengranulated in a rotating pelletizer by spraying with water (up to 10%).The resulting granules are dried in a fluid-bed drier to remove excesswater.

EXAMPLE 16-G

A dusting powder is prepared with the composition as follows:

    ______________________________________    Active ingredient                      1 to 10%    Talc powder-superfine                     99 to 90%    ______________________________________

The ingredients are intimately mixed and further ground as necessary toachieve a fine powder. This powder may be applied to a locus ofarthropod infestation, for example refuse dumps, stored products orhousehold goods or animals infested by, or at risk of infestation by,arthropods to control the arthropods by oral ingestion. Suitable meansfor distributing the dusting powder to the locus of arthropodinfestation include mechanical blowers, handshakers or livestock selftreatment devices.

EXAMPLE 16-H

An edible bait is prepared with the composition as follows:

    ______________________________________    Active ingredient                     0.1 to 1.0%    Wheat flour     80%    Molasses        19.9 to 19%    ______________________________________

The ingredients are intimately mixed and formed as required into a baitform. This edible bait may be distributed at a locus, for exampledomestic or industrial premises, e.g. kitchens, hospitals or stores, oroutdoor areas, infested by arthropods, for example ants, locusts,cockroaches or flies, to control the arthropods by oral ingestion.

EXAMPLE 16-I

A solution formulation is prepared with a composition as follows:

    ______________________________________    Active ingredient                     15%    Dimethyl sulfoxide                     85%    ______________________________________

The active ingredient is dissolved in dimethyl sulfoxide with mixing andor heating as required. This solution may be applied percutaneously as apour-on application to domestic animals infested by arthropods or, aftersterilization by filtration through a polytetrafluoroethylene membrane(0.22 micrometer pore size), by parenteral injection, at a rate ofapplication of from 1.2 to 12 ml of solution per 100 kg of animal bodyweight.

EXAIMPLE 16-J

A wettable powder is prepared with the composition as follows:

    ______________________________________           Active ingredient                     50%           Ethylan BCP                      5%           Aerosil    5%           Celite PF 40%    ______________________________________

The Ethylan BCP is absorbed onto the Aerosil which is then mixed withthe other ingredients and ground in a hammer-mill to give a wettablepowder, which may be diluted with water to a concentration of from0.001% to 2% by weight of the active compound and applied to a locus ofinfestation by arthropods, for example, dipterous larvae or plantnematodes, by spraying, or to domestic animals infested by, or at riskof infection by arthropods, heiminths or protozoa, by spraying ordipping, or by oral administration in drinking water, to control thearthropods, helminths or protozoa.

EXAMPLE 16-K

A slow release bolus composition is formed from granules containing thefollowing components in varying percentages (similar to those describedfor the previous compositions) depending upon need:

Active ingredient

Density agent

Slow-release agent

Binder

The intimately mixed ingredients are formed into granules which arecompressed into a bolus with a specific gravity of 2 or more. This canbe administered orally to ruminant domestic animals for retention withinthe reticulorumen to give a continual slow release of active compoundover an extended period of time to control infestation of the ruminantdomestic animals by arthropods, helminths or protozoa.

EXAMPLE 16-L

A slow release composition in the form of granules, pellets, brickettesor the like can be prepared with composition as follows:

    ______________________________________    Active ingredient  0.5 to 25%    Polyvinyl chloride 75 to 99.5%    Dioctyl phthalate (plasticizer)    ______________________________________

The components are blended and then formed into suitable shapes bymeltextrusion or molding. These composition are useful, for example, foraddition to standing water or for fabrication into collars or eartagsfor attachment to domestic animals to control pests by slow release.

While the invention has been described in terms of various preferredembodiments, the skilled artisan will appreciate that variousmodifications, substitutions, omissions and changes may be made withoutdeparting from the sprit thereof. Accordingly it is intended that thescope of the present invention be limited solely by the scope of thefollowing claims, including equivalents thereof.

What is claimed is:
 1. A compound having the formula: ##STR11## wherein:R₁ is cyano, halogen, formyl, --C(O)R₂, H, or R₂ ;R₂ is C₁ -C₄ alkyl, C₁-C₄ haloalkyl, or cycloalkyl which is unsubstituted or is substitutedwith one or more halogen; R₃ is --S(O)_(n) R₆ ; R₆ is C₁ -C₄ alkyl, C₁-C₄ haloalkyl, or cycloalkyl which is unsubstituted or is substitutedwith one or more halogen; R₇ is --CHR₁₁ R₁₂ ; R₈ is H, C₁ -C₅ haloalkyl;R₁₀ is H, C₁ -C₄ alkyl, or C₁ -C₄ haloalkyl; R₁₁ and R₁₂ are,independently, C₁ -C₄ alkoxy, C₁ -C₄ haloalkoxy, C₁ -C₄ alkylthio, C₁-C₄ haloalkylthio, --NR₈ R₁₀, C₃ -C₈ trialkylsiloxy or cyano; R₁₄ is H,halogen, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, C₁ -C₄haloalkoxy, C₁ -C₄ alkylthio, C₁ -C₄ haloalkylthio, cyano or nitro; R₁₅and R₁₇ are, independently, H or halogen; R₁₆ is halogen, C₁ -C₄ alkyl,C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, C₁ -C₄ haloalkoxy, cyano, nitro,--C(O)R₁₈, or --S(O)_(q) R₁₉ ; R₁₈ is C₁ -C₃ alkyl or C₁ -C₃ haloalkyl;R₁₉ is C₁ -C₃ alkyl or C₁ -C₃ haloalkyl; R₂₀ is H, halogen, cyano,nitro, C₁ -C₄ alkyl, C₁ -C₄ haloalkyl, C₁ -C₄ alkoxy, or C₁ -C₄haloalkoxy; X is a nitrogen atom or C--R₂₀ ; n is 0, 1 or 2; and q is 0,1 or 2; or a pesticidally acceptable salt thereof; provide that: R₁₁ andR₁₂ are always the same expect when R₁₂ is cyano.
 2. A compoundaccording to claim 1 having at least one feature selected from the groupconsisting of:(a) R₁ is cyano; (b) R₁₄ is halogen; (c) each of R₁₅ andR₁₇ is H; (d) R₁₆ is C₁ -C₄ haloalkyl; and (e) X is C--R₂₀.
 3. Acompound according to claim 1 wherein R₁ is cyano, halogen, --C(O)R₂, H,or R₂ ; R₁₄ is halogen; each of R₁₅ and R₁₇ is H; and R₁₆ is C₁ -C₄haloalkyl.
 4. A compound according to claim 1 wherein R₁ is cyano; R₆ isC₁ -C₄ haloalkyl; R₁₁ is C₁ -C₄ alkoxy; R₁₂ is C₁ -C₄ alkoxy or cyano;R₁₄ is halogen; each of R₁₅ and R₁₇ is H; and R₁₆ is C₁ -C₂ haloalkyl.5. A compound according to claim 2 wherein R₁ is cyano; R₆ is C₁ -C₂haloalkyl; R₁₁ is C₁ -C₄ alkoxy; R₁₂ is C₁ -C₄ alkoxy or cyano; R₁₄ ishalogen; each of R₁₅ and R₁₇ is H; and R₁₆ is C₁ -C₂ haloalkyl.
 6. Acompound according to claim 1 wherein R₆ is CF₃ and R₁₆ is CF₃.
 7. Acompound according to claim 2 wherein R₆ is CF₃ and R₁₆ is CF₃.
 8. Acompound according to claim 3 wherein R₆ is CF₃ and R₁₆ is CF₃.
 9. Acompound according to claim 4 wherein R₆ is CF₃ and R₁₆ is CF₃.
 10. Acompound according to claim 5 wherein R₆ is CF₃ and R₁₆ is CF₃.
 11. Thecompound according to claim 1is:3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5dimethoxmetnyl-4-trifluoromethylthiopyrazole;3-cyano-5-{(1-cyano-1-methoxy)methyl}-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylthiopyrazole;3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-dimethoxymethyl-4-trifluoromethylsulfonylpyrazole;3-cyano-5-{(1-cyano-1-methoxy)methyl}-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylsulfonylpyrazole;3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-diethoxymethyl-4-trifluoromethylthiopyrazole;3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-diethoxymethyl-4-trifluoromethylthiopyrazole;or3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-5-diethoxymethyl-4-trifluoromethylsulfinylpyrazole.12. A pesticidal composition comprising a pesticidally effective amountof a compound of formula (I) as defined in claim 1 or a pesticidallyacceptable salt thereof, and a pesticidally acceptable carrier therefor.13. A composition according to claim 12 further comprising apesticidally acceptable surface-active agent.
 14. A method forcontrolling pests at a locus comprising applying to said locus apesticidally effective amount of a compound of formula (I) as defined inclaim 1 or a pesticidally acceptable salt thereof.
 15. A methodaccording to claim 14 wherein said locus is an area used or to be usedfor the growing of crops.
 16. A process for the preparation of acompound of formula (I) as defined in claim 1, said processcomprising:(a) reacting a compound corresponding to formula (I) asdefined in claim 1 expect that R₇ in said compound is formyl, with acompound of the formula

    R.sub.11 --H                                               (VIa)

wherein R₁₁ is as defined in claim 1 other than cyano, to afford thecorresponding compound of formula (I) as defined in claim 1 wherein R₁₁and R₁₂ are other than cyano and are the same; or (b) reacting acompound of formula (I) wherein R₁₁ and R₁₂ are other than cyano and arethe same, with a trialkylsilylcyanide in the presence of an acidcatalyst in a solvent, to afford the corresponding compound of formula(I) wherein R₇ is --CHR₁₁ (CN); optionally followed by converting thecompound thus obtained into a pesticidally acceptable salt thereof.